Preparation and Characterization

of Nanostructured CaCu2.90Zn0.10Ti4O12
Ceramic
Regular Paper

Laxman Singh1, U. S. Rai1 and K. D. Mandal2,*

1 Department of Chemistry, Faculty of Science, Banaras Hindu University, India

2 Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, India
* Corresponding author: kdmandal.apc@itbhu.ac.in
Received 11 May, 2011; Accepted 16 December, 2011

Abstract Nanostructure CaCu2.90Zn0.10Ti4O12 (CCZTO)

electronic ceramic was synthesized by semiwet route.
Theobjectiveofthisrouteistoenablethecalcinationand
sintering processes to go for completion in shorter time
and at lower temperature.The samples were
characterizedbyXRD,TEM,SEMandEDXanalyses.The
crystallite size of the CCZTO ceramic, obtained by XRD
using Debye Scherrer formula, range from 3874nm
whichisingoodagreementwiththeparticlesizeobserved
byTEManalysis.Itwasobservedclearlythatthegrainsize
significantly increased with an increase in sintering
duration. Dielectric measurements were carried out by
LCR meter in the temperature range, 300 500K, at few
selectedfrequencies.Itwasalsoobservedthatthedielectric
constant and dielectric loss of CCZTO are temperature
independent in higher frequency whereas temperature
dependent in low frequency region. The ceramics exhibit
highdielectricconstantof1.35x104at1kHz.

KeywordsCeramics,nanoparticles,dielectricproperties

1.Introduction

Nanosized materials with high dielectric constant are in

thefocusofinterest,notonlyforpurelyacademicreasons
59 Nanomater. nanotechnol., 2011, Vol. 1, No. 2, 59-66

but also because new high r materials are urgently

sought for the further development of modern
electronics. The high dielectric constant material is
desirable to miniaturize capacitor required for
integeratedcircuit.BaTiO3andSrTiO3basedferroelectric
materials exhibit high dielectric constant but these
materials show strong temperature dependence of their
dielectricconstantwhichisnotdesirablefromthedevice
points of view [12]. On the other hand, CaCu3Ti4O12
(CCTO) ceramic has high dielectric constant (r ~ 104
105) independent of frequency (102 106 Hz) and
temperature (100600K) which is desired for
microelectronic applications [34]. Unfortunately, the
CCTO ceramic with giant dielectric constant exhibits
higherdielectriclossthatlimitsitspracticalapplications.
It has been previously reported that the dielectric
propertiesofCCTOarelargelyinfluencedbyfactorssuch
as doping schemes [57] as well as stoichiometric
variations [89]. Recently much work based on partial
substitution at Cu or Ti ions site in CCTO ceramic has
been carried out in order to improve the dielectric
propertiesandtounderstandtheoriginofgaintdielectric
responseinCaCu3Ti4O12ceramic[1012].Partialisovalent
ionic substitutions of Cu by Zn or Mg in CaCu3Ti4O12
ceramic have enhanced the dielectric response due to
modification of its structure [1315]. In these cases,
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compared to the slight change of Cu+/Cu+2 ratio which

also increases Ti+3/Ti+4 ratio, may be the primary factor
for the enhanced dielectric response in CCTO ceramic.
The dielectric constant (r) and loss tangent (tan) of
CCTO are strongly dependent upon the processing
conditions such as sintering temperature [16], sintering
time [17], cooling rate and partial pressure of sintering
atmosphere.Thetraditionalsolidstatereactionmethodis
usually used to prepare crystalline CCTO with starting
materials,CaCO3,CuOandTiO2,instoichiometricratioat
high temperature. The mixtures are calcined for long
duration with several intermediate grindings. This
procedurerequirestediouswork,relativelylongreaction
time and high temperature condition. In addition, some
other secondary phases also appear during synthesis
because of limited atomic diffusion through micrometer
sized grains. On the other hand, the wet chemical
methods provide atomic level mixing of individual
components and result in the formation of
nanocrystalline materials at much lower temperature
compared with solid state reactions. There are many
chemical methods, such as, solgel, coprecipitation,
precursor solution technique and hydrothermal process
[1820] which have already been reported for the
synthesis of CCTO ceramics. But in these chemical
methodsTiisusedasTi(OR)4whichisverycostly.
Inthepresentcommunicationwereportanewsuccessful
route to synthesize nanocrystalline CCZTO by semiwet
routeatlowsinteringtemperatureandshortduration.In
thismethod,themixingprocessisperformedinsolution
state as nitrate solutions along with solid TiO2 which is
very cheap. This is one of the most advantages over the
othermethods.Wealsoreportthedielectricpropertiesof
thisceramic.

2.Experimental

Analytical
grade
chemicals,
Ca(NO3)2.4H2O,
Cu(NO3)2.3H2O, (CH3COO)2Zn.2H2O, titanium dioxide
and citric acid, obtained from Merk, having purity of
99.95 % or better were used as starting materials.
Standardsolutionsofmetalnitrateswerepreparedusing
distilled water. Solutions of the metal nitrates in
stoichiometricamount of these metallic ions were mixed
in a beaker. Calculated amounts of TiO2 and citric acid
equivalenttometalionswereaddedtothesolution.The
solution was heated on a hot plate using a magnetic
stirrer at 7090 oC to evaporate water and then dried at
100120oCinhotairovenfor12htoyieldabluegel.The
gelwascalcinedinairat800oCfor6hinamufflefurnace.
Theresultantmixturewasgroundintofinepowderusing
apestleandmortar.Cylindricalpelletsweremadeusing
hydraulicpress.Thepellets,sinteredat950 oCfor6h,8h
and 12h in air, were abbrebated as CCZTO6h, CCZTO
8h and CCZTO12h, respectively. The densities of
samples were measured by Archimedes method. The

60 Nanomater. nanotechnol., 2011, Vol. 1, No. 2, 59-66

crystallinephasesofthesinteredsampleswereidentified
using an Xray Diffractometer (RichSiefert, ID3000)
employing CuK radiation. The microstructures of the
fractured surfaces were examined using a Scanning
Electron Microscope (SEM, Model JEOL JSM5410). The
Energy Dispersive Xray Analyzer (EDX, Model Kevex,
Sigma KS3) was used for the elemental analysis of the
sintered samples. Transmissions Electron Microscopic
(TEMTechnai12G2,FEI)studiesofthesinteredsamples
were carried out by placing the test sample on carbon
coatedcoppergrid,operatedatanacceleratedvoltageof
120 kV. The dielectric data of Zn doped CCTO ceramics
were collected using the LCR meter (PSM 1735, Newton
4th Ltd, U.K) with variation in temperature at few
selectedfrequencies.

3.Resultsanddiscussion

The relative densities of CaCu2.90Zn0.10Ti4O12 (CCZTO)

ceramics sintered at 6h, 8h and 12h were found to be
91.16,93.34and94.44%,respectively.Itclearlyshowsthat
density increases with sintering time. XRD patterns of
CaCu2.90Zn0.10Ti4O12 sintered at 950 C with different
sinteringtime(6h,8hand12h)areshowninFig.1.XRay
datawereindexedonthebasisofacubicunitcellsimilar
to undoped CCTO (JCPDS 752188), which confirm the
formationofsinglephase.Thelatticeparametersandunit
cell volume, determined using least square refinement
method,aregiveninTable1.

Figure 1. Xray diffraction patterns of CaCu2.90Zn0.10Ti4O12

Ceramicssinteredat950oCfor6h,8hand12h

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Sintering Lattice
Lattice Crystallite Particle
time Parameter Volume size from size
() (3) XRD(nm) from
TEM
(nm)
6h 7.2760.256 385 3813 54 11
8h 7.3210.008 392 6916 73 23
12h 7.3780.015 401 7418 84 15
Table 1. Lattice parameter, unit cell volume and particle size
obtainedfromXRDandTEMforCaCu2.90Zn0.10Ti4O12

Fig. 2 shows the variation of lattice parameter with

sintering time. It is observed from the figure that the
lattice parameter increases with the increase in the
sintering time. The change in unit cell parameter with
timeofannealingisduetoincreaseindensity.Duringthe
heat treatment each crystallite get enough dwelling time
togetproperlycrystallized[21].

Figure2.Varaiationoflatticeparameterwithsinteringtime

Thereisnoevidenceofthepresenceofsecondaryphase.
XRD patterns show the presence of split peaks for the
reflections at 400, 422 and 440. This may be due to
presence of CuK2 along with CuK1 in the Xray
radiations used for the diffraction. This is supported by
thefactthatinallthesereflectionstheintensityofpeaks
duetoCuK2iscloseto50%ofintensityofpeakdueto
CuK1asexpected.Fromthelinebroadeningofthemain
peaks, the crystallite size of the ceramic was estimated
usingtheDebyeScherrerformula[22]:

D=k/cos(1)

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Figure3.SEMimagesofCCZTOceramicssinteredat950 Cfor
(a)6h,(b)8hand(c)12h

where is the wavelength of the Xray, k is a constant

taken as 0.89, is the diffraction angle and is the full
width at half maxima (FWHM). The crystallite size
derivedfromtheXRDdataandTEManalysisaregivenin
theTable1.

Laxman Singh, U. S. Rai and K. D. Mandal: Preparation and Characterization of Nanostructured CaCu2.90Zn0.10Ti4O12 Ceramic

61

smallgrainsize810misobserved.Thegrainsizerange
varies from 1015 m and 1525 m of the ceramics
sintered at 8h and 12h, respectively. It can be seen that
the grain size increased with increase of sintering time
and the correspondingly grain boundary was reduced.
Increasing the sintering time significantly promotes the
grain growth and microstructural densification. The
microstructures show grain growth in the specimen
sintered for 8h and 12h along with some liquid phase.
Additionally,asmallamountofCuOphasewasfoundin
grainboundaryregion.ThisphasewassosmallthatXRD
could not detect. It also seems that with increasing
sinteringtimefrom6h,8hand12hsolidCuOphasestart
melting as shown in Fig. 3(b) and totally melted in at
grain boundary as shown in Fig. 3(c). Copper oxide
present at grainboundary transforms into the liquid
phase during sintering which leads to abnormal grain
growth[2324].

TEM images (Fig. 4) of the CCZTO sintered powders

clearly show that all of the samples consist of
nanocrystalline CCZTO particles whose size increases
withincreasingsinteringtime.Arepresentativemanually
constructed histogram of particle size distribution of
CaCu2.90Zn0.10Ti4O12 (CCZTO8h) is shown in Fig.5. The
particle size of the ceramicssintered at 950 oC for 6h, 8h
and 12h were found to be 5411, 7323 and 8415 nm,
respectively. The crystallite size obtained using Debye
Scherrerformulaissmallerthantheparticlesizeobtained
by TEM. This is due to fact that the Debye Scherrer
formula does not take into account the effect of lattice
strainandinstrumentalfactorsonpeakbroadening.

Figure4.TEMimagesofCCZTOceramicssinteredat950 oCfor

(a)6h,(b)8hand(c)12h

It is clearly observed that the crystallite size increased

withincreasingsinteringduration,whichisconfirmedby
the TEM analysis. The increased crystallite size with
increasing sintering time is mainly due to over grown
grains resulting from the destruction of the grain
boundaries at higher sintering time. These data clearly
showthatthesinteringtimeisresponsibleforincreasing
crystallite size with increasing sintering time of
CaCu2.90Zn0.10Ti4O12ceramic.

Fig. 3 shows SEM images of surface microstructures for

the ceramics sintered at different sintering times. As can
be seen from Fig. 3(a)(c), the microstructures of
CaCu2.9Zn0.1Ti4O12 change significantly with sintering
time.Inspecimensinteredat950Cfor6haporouswith
62 Nanomater. nanotechnol., 2011, Vol. 1, No. 2, 59-66

Figure 5. Histogram of Particle size distribution curve of

CaCu2.90Zn0.10Ti4O12nanoparticlesofCCZTO8h

EDXspectraofCCZTOceramic(Fig.6)sinteredat950 oC
for 6h, 8h and 12h show the presence of Ca, Cu, Zn, Ti
and an extra peak of Pt at 2.15 keV. Pt coating was

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performed by ion beam sputtering for increasing the

The temperature dependence of dielectric constant (r)
conductivity which was necessary to avoid charging or
andlosstangent(tan)oftheCCZTOceramicsinteredfor
chargedupofsamples.TheatomicpercentageofCa,Cu,
6h at different frequencies 0.1, 1, 10 and 100 kHz are
Zn and Ti in the CCZTO ceramics obtained from EDX
showninFig.7.Dielectricconstant(r)exhibitsasteplike
increase from low value 4216 to a giant value 16560 at
dataaregiveninTable2.TheCu/CaratioforCCZTO6h,
temperature above 350K, which is prominent in the low
CCZTO8h and CCZTO12h are 2.75, 2.73 and 2.73,
frequency region and diminishes on increasing the
respectively. The percentage error are found to be 5.45,
frequency.Ataboveroomtemperatureabroaddielectric
6.22and6.22%,respectively.
peak appears between 350K to 425K which also shifts to

higher temperature and decreases in amplitude with

______________________________________________
increasing higher frequencies. It shows a ferroelectric
SinteringAtomic%ofelements
duration_________________________________ relaxor behavior in the ceramic [25]. It is observed from
CaCuZnTiO the Fig. 7 (b) that the corresponding peaks are also
present in the temperaturedependent plot tan. The
_______________________________________________

abovecharacteristicbehaviorsofaferroelectricrelaxoris
usually characterized by diffuse phase transition and
6h4.7613.110.3817.0464.71
strong relaxational dispersion in dielectric constant and

losstangent(tan).
8h6.6918.330.6725.9048.41

Figs.8 & 9 show the variation of dielectric constant and

12h6.7218.370.7024.2949.92
losstangent(tan)withtemperatureat0.1,1,10and100
_______________________________________________
kHz for CCZTO ceramics sintered at 950 C for 8h and
Table2.AtomicpercentageofelementsforCaCu2.90Zn0.10Ti4O12
12h,respectively.Itisclearlyshownfromthefigurethat
(CCZTO)sinteredat950oCfor6h,8hand12h
ferroelectric behavior is not present. It is also observed

that the dielectric constant and dielectric loss of CCZTO

8h and 12h are temperature independent at higher
frequency whereas temperature dependent in the low
frequencyregion.Itisalsonotedfromthefiguresthatthe
valuesofrforCCZTOceramicare1083,4751and4957
at1kHzfor6h,8hand12h,respectively.

It is also inferred that r increases with increasing

sintering time. This is due to the fact that the longer
sintering time produces more oxygen vacancies in the
CCZTOceramicsandresultshighdielectricconstant.Itis
observedfromthefigurethatdielectriclossesat1kHzfor
CCZTO are 1.07, 0.38 and 0.18 for 6h, 8h and 12h,
respectively,atroomtemperature.Averyclearpictureof
thesinteringtimedependenceofdielectricconstantvalue
measured at 10 kHz is shown in Fig. 10. The high
dielectric constant for CCZTO ceramics is due to
interfacial space charge polarization [26]. This interfacial
chargepolarizationarisesduetoaccumulationofcharge
carriers at the interface of semiconducting grains and
insulatinggrainboundary.

Figure 6. EDX spectrum of CCZTO ceramics sintered at 950 oC

for(a)6h,(b)8hand(c)12h

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Laxman Singh, U. S. Rai and K. D. Mandal: Preparation and Characterization of Nanostructured CaCu2.90Zn0.10Ti4O12 Ceramic

63


Figure 7. Variation of r and tan vs temperature of CCZTO
ceramicsinteredat950oCfor6h

Figure 9. Variation of r and tan vs temperature of CCZTO

ceramicsinteredat950oCfor12h

Figure 8. Variation of r and tan vs temperature of CCZTO

ceramicsinteredat950oCfor8h

64 Nanomater. nanotechnol., 2011, Vol. 1, No. 2, 59-66

Figure 10. Dielectric constant value as a function of sintering

timemeasuredat10kHz

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4.Conclusion

It is immensely important that an adequate control of

sintering time and temperature are needed to obtain the
desired microstructure and dielectric properties.
Dielectric constant increases with increasing sintering
timeanddielectriclossdecreases.Itissuggestedthatthe
longersinteringtimemayleadtomoredefectstructures.
Thesizeoftheparticleincreaseswithincreasingsintering
time.Itismainlyduetoformationoflargesizeparticles
as a result of loss of grain boundaries of small size
particles.Thesechangesleadtostabilitytothelargesize
particlesduetolossingrainboundary.

5.Acknowledgements

Authors express their gratitude to Dr. Madhu, Scientist,

InstituteofMedicalScience,BHU,Varanasiforextending
thefacilityforTEManalysis.

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